Methods of avoiding blowhole formation by conditioning through holes and glass

ABSTRACT

A composition and method for cleaning and conditioning a non-conductive surface defined by a through hole in a printed circuit board (PCB) is disclosed. The through hole surface is contacted with the composition of the invention to provide a cleaned and conditioned surface. The clean and conditioned surface is coated with conductive carbon particles (usually graphite) to provide a carbon-coated surface. The carbon-coated surface is electro plated and then soldered using hot solder. Those surfaces that have been soldered and also treated with the composition of the invention exhibit fewer blow hole problems. The composition of the invention comprises carbonates, binders, and resins, and combinations thereof, that improve the adhesion and coverage of a coating containing graphite to a surface defined by a through hole bore or other substrate. (“Through holes” as used herein refers both to through holes and to vias.)

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This is a divisional of application Ser. No. 09/478,587. Theentire specification and all the claims of U.S. Ser. No. 09/478,587 arehereby incorporated by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0002] Not Applicable.

BACKGROUND OF THE INVENTION

[0003] The present invention is directed to printed wiring boards(PWB's) having through holes, or other substrates, made electricallyconductive by applying a conductive coating containing carbon, and moreparticularly graphite. The invention is more particularly directed tomethods of avoiding blowhole formation in printed wiring boards bytreating their through holes with compositions comprising a pH buffer,binders, binding agents, dispersing agents, and combinations thereof,that improve the adhesion and coverage of a conductive coatingcontaining graphite to a surface defined by at least one through holebore or other substrate. (“Through holes” as used herein refers both tothrough holes and to vias.)

[0004] Conductive graphite and carbon black dispersions are used toprovide a superior conductive coating on through hole walls and othernonconductive surfaces. Such dispersions, methods for using suchdispersions to coat through holes, and improved printed wiring boardsfabricated by using such dispersions are defined in U.S. Pat. Nos.5,476,580 and 5,389,270, respectively issued to Thorn et al. on Feb. 14,1995, and Dec. 19, 1995. Both patents referred to in the precedingsentence are incorporated herein by reference in their entireties. Agraphite composition, cleaners, conditioners, and other materials anddirections needed to practice these patents are available under thetrademark SHADOWS from Electrochemicals Inc., Maple Plain, Minn. Othercarbon dispersions containing carbon black or graphite are described,for example, in U.S. Pat. No. 5,139,642.

[0005] Soldering is carried out by coating the through hole walls andother conductive surfaces of a printed wiring board with hot, moltensolder to make electrical connections by wetting and filling the spacesbetween the conductive through hole surfaces and the leads of electricalcomponents which have been inserted through the through holes. Aproperly soldered through hole is filled with solder.

[0006] A problem with “blowholes” occasionally develops after thethrough hole wall has received a conductive coating, has beenelectroplated with copper, and is then suddenly heated, as by contactingit with molten solder. Soldering heats the copper plated through holewalls very quickly. If there are any gaps or voids in the plated copper,moisture in the substrate is vaporized by the hot solder, which can blowsome or all of the solder out of the hole and breach the copper layer.The result is a blowhole or a partially-filled or empty hole, any ofwhich is counted as a soldering defect. It is important that voids donot develop in the copper plate.

[0007] The problem of blowholes in through holes made electricallyconductive by electroless plating, and the solution to blowholes whenthat technology is used, are described in a series of articles publishedin CIRCUIT WORLD, Vol. 12 No. 4 (1986), Vol. 13 No. 1 (1986), and Vol.13 Nos. 2-3 (1987), under the common title, Blowholing in PTH SolderFillets. A related article is C.Lea, The Harmfulness of Blowholes in PTHSoldered Assemblies, CIRCUIT WORLD, Vol.16, No.4, (1990). All thearticles in this paragraph are incorporated herein by reference in theirentirety for their discussion of blowholes in electroless coppertechnology.

[0008] Electroplating copper to the bore of through holes presentsseveral problems as described in U.S. Pat. No. 5,725,807. Chief amongthese is the requirement for a conductive through hole with a coating ofnegligible resistance, uniform thickness, durability, and the ability towithstand solder shock tests. This requirement is met, at least in part,by applying an electrically conductive particulate coating of carbon tothe through hole. The carbon of the particulate coating is either carbonblack or graphite. While the particulate coating described in U.S. Pat.No. 5,725,807 provides distinct advantages and improvements over theprior art, there remains the need to improve the quality of the bindingof the particulate coating, and more particularly the binding of thegraphite particles to the surface of the through hole.

BRIEF SUMMARY OF THE INVENTION

[0009] Accordingly, an object of this invention is to provideimprovements in the cleaning and conditioning of through holes and glassfibers.

[0010] Another object is to provide a printed wiring board conditionerto improve the adhesion of carbon particles to the conditioned surface.

[0011] Yet another object is to provide a substrate conditioner thatimproves the continuity of coverage of carbon particles on a throughhole wall or other substrate.

[0012] A further object is to provide a method of soldering throughholes to produce fewer blowholes.

[0013] At least one of these objects is addressed, in whole or in part,by the present invention.

[0014] We have discovered that the binding and continuous coverage ofcarbon particles to a surface defined by at least one through hole isgreatly improved by the addition of an ingredient selected from a pHbuffer, a binder, a dispersant, or combinations thereof, to aconditioning formulation applied to a substrate before the carbonparticles are applied.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

[0015] The following is a brief description of the drawing which ispresented for the purpose of illustrating the invention and not forpurposes of limiting the same.

[0016]FIG. 1 shows a schematic flow chart depicting one aspect of thepresent invention.

[0017]FIG. 2 shows the chemical steps in one aspect of the presentinvention.

DETAILED DESCRIPTION OF THE INVENTION

[0018] While the invention will be described in connection with one ormore embodiments, it will be understood that the invention is notlimited to those embodiments. On the contrary, the invention includesall alternatives, modifications, and equivalents as may be includedwithin the spirit and scope of the appended claims.

[0019] The present invention is directed to a conditioning compositionincluding, beyond the usual conditioning ingredients, one or more of thefollowing: a binding agent, a pH buffer, a dispersing agent, andcombinations thereof, that improve the adhesion and coverage of aconductive coating containing graphite to a surface defined by at leastone through hole bore or other substrate.

[0020] Cleaning compositions, conditioning compositions, andcleaner/conditioner compositions contemplated for use in the inventionare described in detail in U.S. Pat. Nos. 5,725,807 and 5,690,805, whichare incorporated by reference, and in material incorporated therein byreference.

[0021] Some of the useful ingredients of such compositions are describedbelow.

[0022] Conditioning Agent

[0023] In the conditioning step, the substrate is contacted with aconditioning agent, which is a substantive material, commonly a cationicmaterial such as a polyamidoamine, a cationic polymer, a cationicsurfactant, or the like. The conditioning agent is applied as anadhesion promoter so the substrate will be attractive to the anionicparticles of carbon which are later applied by contacting the substratewith a carbon dispersion.

[0024] The conditioner can be an alkaline aqueous solution or dispersionof a conditioning agent selected from the group consisting of:

[0025] SANDOLEC CF

[0026] SANDOLEC CU

[0027] SANDOLEC CS

[0028] SANDOLEC CL

[0029] SANDOLEC CT

[0030] CALLAWAY 6818

[0031] CYASTATSP

[0032] CYASTAT LS

[0033] CYASTAT SN

[0034] CYANAMER A-370

[0035] MAGNIFLOC 496

[0036] DAXAD CP2

[0037] PRIMAFLO C C3

[0038] CAT-FLOC

[0039] CAT-FLOC T

[0040] RETEN 210

[0041] POLYTEC 7M

[0042] PERCOL 727

[0043] PERCOL 763

[0044] OCTOPOL SDE-25

[0045] OCTOPOL SDM-40

[0046] GLO-CLEAR 2202

[0047] GLO-CLEAR 2220

[0048] GLO-CLEAR 2283

[0049] PRIFRAC 2990

[0050] ALUBRAFSOFT GSS

[0051] FIBRABON 35

[0052] DENSEFLOC 30

[0053] CALLAWAY 6817

[0054] CALLAWAY 6831

[0055] and combinations of those conditioners.

[0056] A conditioner will also commonly contain a base. The basescontemplated herein include lower alkanol amines (lower alkanol beingdefined as 1- to 4-carbon alcohol moieties), such as ethanolamines, forexample mono-, di- or triethanolamine; alkali materials generally, suchas alkali metal hydroxides, carbonates, and bicarbonates, for examplepotassium hydroxide, carbonate, or bicarbonate; other materials capableof raising the pH of the composition, preferably to at least about 9;and mixtures of such materials.

[0057] Binding Agent

[0058] One component of some of the compositions of the presentinvention is a water soluble or dispersible binding agent for bindingthe carbon particles. The binding agent is believed to assist thedispersed carbon particles in adhering to the surface of thenon-conductive (i.e., dielectric) substrate which is to be madeconductive for electroplating. The binding agent may be present as fromabout 0% to about 15% by weight, or from about 0.2 to about 10% byweight, or from about 0.5% to about 6% by weight, or from about 1.5% toabout 3% by weight, of the composition.

[0059] The binding agent of the present invention is preferably anynatural or synthetic polymer, polymerizable monomer, or other viscous orsolid material (or precursor thereof) that is capable of both adheringto the carbon particles and of receiving an anionic dispersing agent (asdescribed below). For example, the binding agent may be a water solubleor water dispersible material selected from the group consisting ofmono- and polysaccharides (or, more broadly, carbohydrates) and anionicpolymers. Typically, for purposes of this invention, a 2% by weightaqueous test solution of the binding agent will have a viscosity withinthe range of 25-800 cps at 25° C., although other concentrations of thebinding agent and other viscosities of the complete through hole coatingcomposition are also contemplated herein.

[0060] Monosaccharide binding agents contemplated for use herein includetetroses, pentoses, and hexoses. Polysaccharide (which for the presentpurposes includes disaccharide and higher saccharide) binding agentscontemplate for use herein include sucrose (from beets, sugarcane, orother sources), maltose, fructose, lactose, stachyose, maltopentose,dextrin, cellulose, corn starch, other starches, and polysaccharidegums. Polysaccharide gums contemplated for use herein include agar,arabic, xanthan (for example, KELZAN industrial grade xanthan gum,available from the Kelco Div. of Merck & Co, Inc. of Rahway, N.J.),pectin, alginate, tragacanath, dextran, and other gums. Derivativepolysaccharides contemplated for use herein include cellulose acetates,cellulose nitrates, methylcellulose, and carboxymethylcellulose.Hemi-cellulose polysacharides contemplated for use herein included-gluco-d-mannans, d-galacto-d-gluco-d-mannans, and others. Anionicpolymers contemplated herein include the alkylcelluloses orcarboxyalkylcelluloses, their low- and medium-viscosity alkali metalsalts. Examples include methyl cellulose (CAS registry no.: 9004-67-5);sodium carboxymethylcellulose, or “CMC”; CAS register no.: 9004-32-4;cellulose ethers; and nitrocellulose. Examples of such anionic polymersinclude KLUCEL hydroxypropylcellulose; AQUALON CMC 7L sodiumcarboxymethylcellulose, and NATROSOL hydroxyethyl cellulose, which areall commercially available from Aqualon Company of Hopewell, Va.;ethylcellulose, available from Hercules of Wilmington, Del.; METHOCELcellulose ethers, available from Dow Chemical Co., Midland, Mich.; andnitrocellulose, which is also available from Hercules. Sodium CMC is ananionic water soluble polymer derived from cellulose. Sodium CMC isbelieved to act as a thickener, binder, stabilizer, protective colloid,suspending agent, and rheology, or control flow, agent.

[0061] The acrylics contemplated herein for use as binding agentsinclude polymerizable monomers and polymers, for example, emulsionpolymers commonly known as acrylic latices. The monomers includeacrylamide, acrylonitrile, acrylic acid, methacrylic acid, glycidylmethacrylate, and others. The acrylic polymers include polymers of anyone or more of the foregoing monomers; polyacrylamide polymers such asSEPARAN NP10, SEPARAN MGL, SEPARAN 870, and SEPARAN MG200 polymers;polyacrylic acid; acrylic ester polymers such as polymethyl acrylate,polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate,polybutyl acrylate, polyisobutyl acrylate, polypentyl acrylate,polyhexyl acrylate, polyheptyl acrylate, polyoctyl acrylate, andpolyisobornyl acrylate; and other polyacrylates. Suitable acrylicsavailable to the trade include NALCO 603, PURIFLOC C31, and ACRYSOL®acrylics sold by Rohm and Haas Company of Philadelphia, Pa.

[0062] Other binding agents are also contemplated herein. The vinylresins contemplated herein include polyvinyl acetates, polyvinyl ethers,and polyvinyl chlorides. The pyrrolidinone resins contemplated hereininclude poly(N-vinyl-2pyrrolidinone). Representative trade materials ofthis kind are PVP K-60 resin, PVP/VA E335 resin, PVP/VA 1535 resin, andother resins sold by GAF Corporation. The polyols contemplated hereininclude polyvinyl alcohols. The polyvinyl alcohols contemplated hereininclude ELVANOL 90-50, ELVANOL HV, ELVANOL 85-80, and others.

[0063] Cationic resins and other materials contemplated for use hereinas binding agents include polyethylenimine, methylaminoethyl resins,alkyltrimethylamnonium chlorides, and others. Esters of olefinicalcohols, aminoalkyl esters, esters of ether alcohols, cycloalkylesters, and esters of halogenated alcohols are also contemplated for useas binding agents. Polyethylene oxides, such as materials availableunder the trade names NSR N-10, NSR N3000, and NSR 301 from UnionCarbide Corp., are contemplated herein.

[0064] Still more binding agents contemplated herein include epoxyresins, cresol novolac resins, phenol novolac resins; epichlorohydrinresins; bisphenol resins; phenolic resins, such as DURITE AL-5801A resinavailable from Borden Packaging and Industrial Products of Louisville,Ky.; and natural resins and polymerizable materials such as damar,manila, rosin gum, rosin wood, rosin tall oil, and others.

[0065] A practical upper limit to the amount of binding agents used iscontemplated to be that amount which materially interferes with theconductivity of the resulting conductive coatings by diluting theconductive solids in the composition after it is deposited as a film.

[0066] Dispersing Agent

[0067] Another component of some of the compositions of the presentinvention is an anionic dispersing agent. The anionic dispersing agenthas a molecular weight less than about 1000 Daltons, so it is asubstantially smaller molecule than the binding agent.

[0068] The anionic dispersing agent has a hydrophobic end and ahydrophilic (anionic) end. It flnctions by surrounding the bound carbonparticles and causing the bound particles to disperse. It is believedthat the hydrophobic end of each anionic dispersing agent is attractedto the hydrophobic region of the binding agent, thereby causing theanionic end of the anionic dispersing agent to stick out into theaqueous surrounding dispersing medium. When each bound carbon particlehas sufficient dispersing agent bound to it, the sphere of anioniccharges surrounding each particle causes the particles to repel oneanother, and thus, to disperse.

[0069] The amount of anionic dispersing agent that is contemplated inthe composition of the present invention is an amount sufficient tocause the bound carbon particles to disperse in the aqueous dispersingmedium. The amount of dispersing agent that is used is dependent uponthe size of the carbon particle and the amount of binding agent boundthereto. As a general rule, smaller carbon particles require lesseramounts of dispersing agent than would be required to disperse largerparticles. To determine the amount of dispersing agent that is requiredin any particular case, one of ordinary skill in the art can begin byadding ever increasing amounts of dispersing agent to the bound carbonparticles until a sufficient amount is added to cause the particles todisperse. This amount of dispersing agent is the minimum effectiveamount of dispersing agent. Increasing amounts of dispersing agent couldbe added without adversely affecting the dispersion of the carbonparticles. To ensure that the particles remain dispersed, one could adda ten percent greater amount of dispersing agent than is needed. Thus,for purposes of the present invention, the amount of anionic dispersingagent that is used in the composition of the present invention must bean amount that is effective for dispersing the bound carbon particles.For example, the anionic dispersing agent may be present as from about0% to about 10% by weight, alternatively from about 0.01% to about 5% byweight, alternatively from about 0.1% to about 2% by weight of thecomposition.

[0070] A practical upper limit to the amount of anionic dispersingagents used is contemplated to be that amount which materiallyinterferes with the conductivity of the resulting conductive coatings bydiluting the conductive solids in the composition after it is depositedas a film.

[0071] Suitable anionic dispersing agents include acrylic latices,aqueous solutions of alkali metal polyacrylates, and similar materials.Specific dispersing agents contemplated herein include ACRYSOL® I-1955,ACRYSOL® G110, and ACRYSOL® I-545 dispersing agents, all of which arecommercially available from the Rohm and Haas Co., Philadelphia, Pa. TheACRYSOL® dispersing agents may be used alone or together.

[0072] Buffers

[0073] The composition and method of the present invention is capable ofbeing run over a wide pH range. The present composition may have a pHwithin the range of from about 4 to about 14. An alternative pH range isfrom about 9 to about 11, another is from about 9.5 to about 10.5, andstill another is from about 10.7 to about 11.

[0074] Preferably, the pH is maintained by a pH buffer. The bufferfunctions by precluding or minimizing changes in pH such as may occurduring the course of a run as a large number of boards are treated withthe composition of the present invention. The maintenance of a constantor nearly constant pH insures the composition is reproducible from boardto board. Another advantage of using a buffer system is that thenormalities of one or more buffer components can be measured andadjusted to maintain proper process control.

[0075] A pH in the preferred range can be provided by acarbonate-bicarbonate buffer. The use of other pH buffering systems,such as phosphate, acetate, borate, barbital, and the like, are wellknown in the art. The anions of the buffer may be associated with anysuitable cation, such as an alkali metal cation, such as sodium,potassium, or lithium; or an ammonium cation.

[0076] Cleaning/Conditioning

[0077] The present invention can also be carried out by using a singletreatment both to clean and condition a nonconductive substrate. In theevent a combined cleaner/conditioner is to be made, cleaning ingredientscan be added to the conditioner. The principal cleaning ingredientscontemplated herein, beyond the ingredients specified previously for aconditioner formulation, are one or more of the following: nonionicsurfactants, glycols, or chelating agents.

[0078] The nonionic surfactants contemplated herein include thefollowing:

[0079] TERGITOL 15-S-9

[0080] TERGITOL 15-S-15

[0081] NEODOL 25-12

[0082] IGEPAL CO730

[0083] IGEPAL CO887

[0084] TERGITOL NP-15

[0085] MIRANOL 2M-CA

[0086] MIRANOL 2M-CT

[0087] MIRANOL CM-SF

[0088] MIRANOL J2M-SF

[0089] MIRANOL S2M-SF

[0090] and combinations of those surfactants.

[0091] The alkylene glycols contemplated herein include 1- to 4-carbonalkylene glycols and their dimers and oligomers. Specific alkyleneglycols contemplated herein include ethylene glycol, propylene glycol,butylene glycols, diethylene glycol, triethylene glycol and mixtures ofsuch materials.

[0092] The chelating agents contemplated herein include alkali metalsalts of ethylenediaminetetraacetic acid (EDTA), for example, sodiumEDTA (Na₄EDTA). Other suitable chelating agents may also be readilyfound by one of ordinary skill in the art.

[0093] Referring to FIGS. 1 and 2, the cleaning and conditioning of thesubstrate forms part of a step by step procedure in which a suitablesubstrate might be placed in a bath containing the cleaner/conditioner,followed by a rinsing step, followed by a carbon coating compositionsuch as SHADOW® 1 or SHADOW® 2, followed by the electroplating step.

[0094] Cleaner/conditioners and conditioners according to the presentinvention have been found to reduce the problem of blowholes, which theinventors believe is related to the formation of voids.

[0095] It is believed that voids occur because the conductive coatingapplied to the substrate is deficient in some manner. Where theconductive coating, for example a graphite coating, fails to cover thesubstrate adequately, the copper electroplating of the conductivecoating results in voids. To avoid voids, the conductive coating must beapplied evenly and consistently to the substrate and remain in place. Itis believed that adhesion and coverage of the conductive coating to thesurface of the substrate are important factors in minimizing theoccurrence of blowholes.

[0096] While the invention is not limited by any theory as to why thecomposition of the invention improves the coverage and adhesion of acarbon coating to the surface of the through hole, the inventors believethe composition functions as follows. When the composition is contactedwith the non-conductive surface of the through hole, a thin layer of thecomposition is believed to adhere to the surface by means of largelynon-covalent interactions with the surface of the substrate.

[0097] It is believed that when the conductive carbon composition iscontacted with the substrate that has been treated with the compositionof the invention, the carbon adheres to the surface in a continuous andeven manner to achieve good coverage. Subsequent copper electroplatingof the conductive carbon layer produces few or no voids. Soldering thecopper plated through holes of the invention results in few or noblowhole problems.

[0098] One way for assessing the effectiveness of the cleaning andconditioning agents is by performing the hot oil thermal shock test. Hotoil is substituted for hot solder to provide a method to detect unwantedvoids in copper plated substrate, particularly copper plated throughholes. The copper plated through hole is contacted with the hot oil andthe thermal shock causes moisture trapped in any voids to vaporize.Through holes and vias subjected to the hot oil test may be sectionedand examined microscopically for voids. Alternatively, the through holesmay be conventionally electroplated as printed wiring boards would beprocessed, the through holes then sectioned by cutting the boards, andthe plated through holes evaluated for lumpiness, pullaway, and voidsunder microscopic examination.

[0099] The effectiveness of the cleaning conditioning process of thepresent invention was partly evaluated by assessing the degree ofcoverage of the graphite using a back lighting technique and furtherevaluated by a hot oil test procedure with an accompanying blowholeevaluation.

Back Lighting Technique

[0100] In the back lighting technique a treated substrate is examined atlow magnification to assess the degree of coverage in terms ofbacklight-values that can range from 1 to 10 or 10% to 100%.

The Hot Oil Test Procedure

[0101] The hot oil test procedure and accompanying blowhole evaluationis described here with reference to SHADOW® 2 graphite dispersion acleaner/conditioner formulation. The hot oil test procedure andaccompanying blowhole evaluation can be carried out by making upseparate one liter amounts (with DI, deionized water) of SHADOW® 2 (8%)one part (available from Electrochemicals Inc.) and one part DI toprovide a “SHADOW® bath”; microetch solution: 75 g/l sodium persulfate &1% v/v sulfuric acid; Acid Cleaner 7A 15% v/v (available fromElectrochemicals Inc.) With these solutions on hand place one to fourcoupons (i.e. substrate) on copper hooks and perform the steps listed inTable 4: TABLE 1 Step Time Temperature 1. cleaner/conditioner 5 min. (±1min.) 135° F. (±5° F.) 2. Running water rinse 45 sec (±15 sec) Ambient3. SHADOW ® bath 5 min (±1 min.) Ambient 4. Air brush with n/a Ambientcompressed air 5. Oven dry 15 min. (±1 min.) 200° F. (±5° F.) 6.microetch 1 min. (±30 sec) Ambient 7. Running water rinse sufficient toremove Ambient remnants of SHADOW ® bath 8. Acid Cleaner 7A 3 min. (±30sec) 130° F. (±5° F.) 9. Running water rinse 45 sec (±15 sec) Ambient10. Copper plating bath 75 min. Ambient (current @ 10.5 A for 4 coupons)11. Running water rinse 45 sec (±15 sec) Ambient 12. Air Brushsufficient to remove Ambient access water

Blowhole Evaluation

[0102] After step 12 of Table 4 is complete a blowhole evaluation isperformed to determine the number of holes that outgas. To ensureaccurate counts, a VCR and camera may be used. The blowhole evaluationcan be carried out, as follows:

[0103] (i) Heat a quantity of oil (source for this oil etc.) sufficientto cover the coupons (heat to 235° C.). Use stir bar to stir oil.

[0104] (ii) Set up a suitable camera with VCR, check focus of camera byfocusing on heated oil. Start camera and VCR.

[0105] (iii) Turn off stir bar, using tongs and protective face maskcarefully place the coupon in the hot oil. Record the coupon using thecamera for about 5 seconds.

[0106] (iv) Remove the coupon from the hot oil. Stop recording.

[0107] (v) Rewind VCR tape and play the recording on a monitor byadvancing in 3 second (±{fraction (1/30)} sec.) intervals. Count thenumber of holes that were outgassing and the total number of holes. The“Hot Oil Test %” result is calculated as follows:

Hot Oil Test %=[(number of holes that were outgassing)÷(total number ofholes)]*100.

[0108] The following examples represent specific but nonlimitingembodiments of the present invention:

EXAMPLE 1

[0109] The effect of different cleaning and conditioning agents(“CL/COND”) with and without binders on the degree of coverage achievedwith the SHADOW® 1 Colloidal Graphite Dispersion was examined. Theformulations and resulting observations are set out in Table 2. TABLE 2SHADOW ® 1 and CL/COND (with/without Binders) Coverage in 10 minute Runplating # Formulation*¹ Scale 1-10 Comments 1 Colloidal Graphite  9.0 Nobinder Dispersion One part SHADOW ® 1, One part DI*² water CL/CONDCL/COND III*³ 20% v/v 2 Colloidal Graphite 10.0 ACRYSOL ® I-1955Dispersion Perfect binder in combination One part with CL/COND IIISHADOW ® 1, provides the best One part DI* water coverage with CL/CONDSHADOW ® 1 CL/COND III, 20% v/v ACRYSOL ® I-1955 25 ml/500 ml DI

EXAMPLE 2

[0110] The effect of different cleaning and conditioning agents(“CL/COND”) with and without binders on the degree of coverage achievedwith AQUADAG E, sold by Acheson Colloids Company, P.O.box 611757, PortHuron, Mich., Asbury Graphite Mills Inc., Asbury, N.J, was examined. Theformulations and resulting observations are set out in Table 3. TABLE 3AQUADAG E and CL/COND (with/without Binders) Coverage in 10 Run minuteplating # Formulation Scale 1-10 Comments 1 Colloidal GraphiteDispersion 8.5-9.0 No binder in AQUADAG E 115 ml Pin voidscleaner/conditioner. make up to 500 ml with DI small patch CL/COND voidswere CL/COND III 20% v/v observed. 2 Colloidal Graphite Dispersion7.0-8.0 ACRYSOL ® I- AQUADAG E 115 ml Big patch 1995 binder as make upto 500 ml with DI voids the sole CL/COND CL/COND observed. does notpromote ACRYSOL ® I-1955 good coverage with 50 ml/500 ml DI AQUADAG E. 3Colloidal Graphite Dispersion 9.0 ACRYSOL ® G110 AQUADAG E 115 ml Onlypin binder works well make up to 500 ml with DI voids. Better inconjunction with CL/COND than run #1 monoethanolamine MEA 5 ml/500 DI asa ACRYSOL ® G110 cleaner/conditioner. 10 ml/500 DI 4 Colloidal GraphiteDispersion 9.0-9.7 CMC binder n AQUADAG E 115 ml Only pin CL/COND helpsto make up to 500 ml with DI voids, better promote coverage. CL/CONDthan run #1 CL/COND III 20% v/v CMC 5 g/500 ml Tamol 9GO 5 ml/500

EXAMPLE 3

[0111] The effect of different cleaning and conditioning agents(“CL/COND”) with the SHADOW® 1 and SHADOW® 2 formulations was examined.The formulations and resulting observations are set out in Table 4.TABLE 4 CL/COND with Shadow 1 vs. CL/COND with SHADOW ® 2 Coverage inHot 10 minute Oil plating Test Run Formulation Scale 1-10 % Comments #1Colloidal Graphite A) 9.0 to 9.5 A) 60 No binder Dispersion A” incleaner/ 1 part SHADOW ® 2 conditioner. (8% conc.) 1 part DI B) 9.0 to9.5 B) 16 Colloidal Graphite Dispersion “B” 2 parts Shadow 1 1 part DICL/COND for A & B CL/CONP III 20% v/v #2 Colloidal Graphite A) 9.0 A)CL/COND III Dispersion A” 100 with 1 part SHADOW ® 2 ACRYSOL ® (8%conc.) B) 10.0 B) I-1955 dispersant 1 part DI 5.5 provides betterColloidal Graphite Coverage and Hot Dispersion “B” Oil Test results 2parts Shadow 1 with Shadow 1 1 part DI than the same for- CL/COND for A& B mulation provides CL/COND III 20% v/v without a binder 50 mls ofACRYSOL ® in the cleaner/ I-1955 (50 mls/l) conditioner. #3 ColloidalGraphite A) 9.5-9.7 A) 21 No binder in Dispersion A” cleaner/ 1 partSHADOW ® 2 conditioner. (8% conc.) B) 9.5 B) 36 1 part DI ColloidalGraphite Dispersion “B” 2 parts Shadow 1 1 part DI CL/COND for A & B(per liter): 1 g KOH (86%), 25.0 g Grafquat HS 100 25.5 g Neodol 91-8,50 mg Mercapto Benzo Thiazole (“MBT”), 2.0 g Versene 100 ®, DI to 1.0liter #4 Colloidal Graphite  9.7   8 CMC 7L with Dispersion SHADOW ® 2 1part SHADOW ® 2 and CL/COND III (8% conc.) with 1 part DI ACRYSOL ® 0.4g/500 ml CMC* 7L I-1955 dispersant CL/COND provide good Hot CL/COND III20% v/v Oil Test result. ACRYSOL ® I-1955 (Compare to Run 50 ml/l #2A).#5 Colloidal Graphite 10.0 7.0 CL/COND with Dispersion ACRYSOL ® I-SHADOW ® 2 (8% 1955 dispersant conc.): 350 ml and CMC 7L DI water to 500ml binder provides CL/COND (1 liter) good Hot Oil CL/COND III 20% v/vTest with (200 mls) SHADOW ® 2. ACRYSOL ® I-1955 (Compare to Run 50 mls#2A). CMC 7L 0.5 g DI to 1 liter

[0112] The foregoing examples show that better coverage and fewer blowholes can be obtained by adding a binder and/or a dispersing agent, asdefined above, to the cleaner/conditioner or conditioner formula appliedbefore a carbon containing is applied.

[0113] While the invention is described above in connection withpreferred or illustrative embodiments and examples, they are notintended to be exhaustive or limiting of the invention. Rather, theinvention is intended to cover all alternatives, modifications andequivalents included within its spirit and scope of the invention, asdefined by the appended claims.

1. A method for providing a soldered surface that is substantially freeof blow-holes, comprising the steps of: (a) contacting a surface with aconditioning composition to provide a conditioned surface, saidconditioning composition comprising a cationic conditioning agent and atleast one ingredient selected from an anionic dispersing agent and abinder; (b) contacting said conditioned surface with a conductive carboncoating to provide a carbon coated surface; (c) electroplating saidcarbon coated surface to provide an electroplated surface; and (d)soldering said electroplated surface to provide a soldered surface thatis substantially free of blow-holes.
 2. The composition of claim 1,wherein said at least one ingredient comprises an anionic dispersingagent.
 3. The composition of claim 1, wherein said at least oneingredient comprises a binder.
 4. The composition of claim 1, whereinsaid at least one ingredient comprises sodium carboxymethylcellulose.